US3337512A - Product and process for preparing poly(2, 6-xylylsulfonates) - Google Patents

Product and process for preparing poly(2, 6-xylylsulfonates) Download PDF

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US3337512A
US3337512A US429652A US42965265A US3337512A US 3337512 A US3337512 A US 3337512A US 429652 A US429652 A US 429652A US 42965265 A US42965265 A US 42965265A US 3337512 A US3337512 A US 3337512A
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Prior art keywords
xylenol
sulfonyl chloride
poly
product
polymer
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US429652A
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Walter L Hall
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General Electric Co
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General Electric Co
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Priority to US429652A priority Critical patent/US3337512A/en
Priority to GB2556/66A priority patent/GB1126004A/en
Priority to NL6600874A priority patent/NL6600874A/xx
Priority to DE19661595720 priority patent/DE1595720A1/de
Priority to FR48006A priority patent/FR1466814A/fr
Priority to US631849A priority patent/US3530177A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/24—Polysulfonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof

Definitions

  • This invention relates to the new chemical compounds, 2,6-xylenol-3-sulfonyl chloride and 2,6-xylenol-4-sulfonyl chloride, mixtures thereof and to polymers produced by the self-condensation of these compounds whereby the sulfonyl chloride of one molecule reacts with the hydroxyl group of another molecule splitting off hydrogen chloride and forming a poly(2,6-xylylsulfonate).
  • the above new chemical compounds are the subject matter of my divisional application Ser. No. 631,849, filed Apr. 19, 1967, and assigned to the same assignee as the present invention.
  • Polymeric aromatic sulfonates have been prepared by the reaction of a biphenol and an aromatic disulfonyl halide.
  • this reaction in order to obtain high molecular weight products, it is necessary to carry out the reaction in a two-phase reaction in which the aromatic disulfonyl chloride is in an organic phase and the diphenol is dis solved in an aqueous phase with alkali. It is further necessary that equal molar amounts of the two reactants be used to obtain high molecular weight products.
  • 2,6-xylenol also named 2,6dimethylphenol
  • 2,6-xylenol can be readily chlorosulfonated with chlorosulfonic acid to produce a mixture of 2,6-xylenol-4- sulfonyl chloride and 2,6-xylenol-3-sulfonyl chloride.
  • This mixture of compounds can be used as prepared or the mixture of the two compounds can be readily separated into the two isomers prior to making the polymeric condensation product.
  • These two isomeric 2,6-xylenolsulfonyl chlorides can also be readily produced by reacting the corresponding sulfonic acids with a chlorinating agent such as thionyl chloride.
  • the organic solvent is a solvent for both the starting xylenolsulfonyl chloride and the final polymeric product.
  • I can prepare the two isomeric 2,6-dichlorophenolsulfonyl chlorides in the same way that I can form the two isomeric 2,6-xylenolsulfonyl chlorides, I have found that self-condensation of these chlorophenolsulfonyl chlorides leads only to the formation of low molecular weight, brittle, cyclic polymers which are completely unsatisfactory for the making of useful, shaped, polymeric products. Unfortunately, the cyclic materials cannot be further polymerized to higher molecular weight polymers by any known means.
  • 2,6-xylenol-4-sulfonyl chloride is by snlfonation of 2,6-xylenol to form 2,6- xylenol-4-sulfonic acid which is isolated in the form of its alkali metal salt, for example, the sodium salt, following the procedure described by P. Karrer and P. Leiser, in Helv. Chim. Acta 27, 678 (1944).
  • the method of preparing 2,6-xylenol-3-sulfonyl chloride is as a mixture with 2,6-xylenoL4-sulfony1 chloride followed by separation of the isomers.
  • I have determined that when 2,6-xylenol is chlorosulfonated that the product is a mixture of approximately mole percent 2,6xylenol- 3-sulfonyl chloride and 15 mole percent 2,6-xylenol-4- sulfonyl chloride.
  • This mixture can be used as such or it can be separated to isolate the 2,6-xylenol-3-sulfonyl chloride, by fractional crystallization and sublimation from the other isomer.
  • an organic solvent which is a solvent for both the 2,6- xylenolsulfonyl chloride and the poly(2,6-xylyl sulfonate).
  • These solvents should be nonreactive with the sulfonyl chloride and phenolic hydroxyl groups, and should be capable of being made anhydrous.
  • Typical solvents which are satisfactory are tetrahydrofuran, tetrachloroethane, nitrobenzene, etc. As long as the solvent meets the requirements of solubility for both the starting and final product, and can be made anhydrous. Any organic solvent is satisfactory. Of the various solvents I have tried, nitrobenzene is the preferred solvent and leads to the highest molecular weight products.
  • the sulfonyl halide group of one molecule readily reacts with the hydroxyl group of another molecule to produce an essentially linear poly(2,6-xylylsulfonate) according to the following equation wherein the sulfur atom on one benzene ring is joined to the oxygen atom on the adjacent benzene ring of the polymer molecule.
  • n represents the number of molecules of 2,6-xylenolsulfonyl chloride which self-condense to form one molecule of the polymer.
  • the actual number of molecules of the monomer in the polymer is not constant for each polymer molecule but is a distribution whose average number is known as the average degree of polymerization which multipled by the molecular weight of the repeating unit, gives the number average molecular weight of the polymer. Since my polymers have film and fiber-forming properties, they have an average molecular weight of at least 10,000 and generally higher which would mean that n is an average of at least 55 and generally is 100 or higher.
  • Example I This example illustrates the preparation of a mixture of 2,6-xyleno1-3-sulfonyl chloride and 2,6-xylenol-4-sulfonyl chloride, and the separation of 2,6-xylenol-3-sulfonyl chloride from this mixture.
  • the precipitate was isolated by filtration. After washing several times with distilled water, the precipitate was vacuum dried at room temperature. The crude product weighed 30.9 g. The solid was extracted with hot ligroin and the insoluble material was recrystallized from hot mixture of 1 volume of toluene to 4 volumes of ligroin. Recrystallization a second time from the same solvent mixture yielded a white solid. The needle-like crystals, which were isolated, were vacuum dried and sublimed at 52 C. under 5 microns pressure. The white sublimed solid had a melting point of 90 C.
  • Elemental analysis showed the material to be 43.7% C, 4.1% H, and 15.8% C1, which is in agreement with the calculated values of 43.5% C, 4.1% H, and 16.1% C1.
  • the molecular weight as determined by the Mechrolab osmometer was 219i5% using chloroform as the solvent. Both the NMR and IR spectra were in accordance with the chlorosulfonyl group being in the 3-position adjacent to the methyl group. All these data show that the product was 2,6-xylenol-3-sulfonyl chloride.
  • the NMR spectrum showed the presence of two different methyl groups at 2.35 and 2.66 in the ratio of 1 to 1 and an AB pattern for 2 aromatic hydrogen atoms between 7.06 and 7.76.
  • the phenolic proton appeared at 5.16.
  • the infrared spectrum showed two strong bands at 810 and 860 cm.- characteristic of l, 2, 3, 4 benzene ring substitution, which is the order of substitution in 2,6-xylenol-3-sulfonyl chloride if numbering is started at the methyl group in the 6-position.
  • Example II This example illustrates the preparation of 2,6-xylenol- 4-sulfonyl chloride.
  • Sodium 2,6-xylenol-4-sulfonate was prepared by the method of Karrer and Leiser, (previously referenced).
  • a solution of 22.4 g. of the sodium salt in 40 ml. .of dimethylformamide was cooled to 0 C.
  • 33.0 g. of thionyl chloride was added dropwise over a 10 minute period. The cooling bath was removed whereupon the temperature rose to 39 C. due to the exothermic nature of reaction. After a total reaction time of 52 minutes, the reaction mixture was added cautiously to 100 g. of ice.
  • the white solid which formed was isolated by filtration and washed several times with distilled water. After vacuum drying at room temperature, the isolated solid which weighed 19.8 g. was dissolved in a minimum amount of toluene and the solution dried with anhydrous sodium sulfate. An approximately equal volume of n-hexane was added to the dried solution. The solution was then cooled to 0 C. The crystals which formed, were isolated by filtration and vacuum dried to yield 13.5 g. of product which had a melting point of 135:1 C.
  • the NMR spectrum show 1 methyl hydrogen peak at 2.46, a single aromatic hydrogen peak at 7.15 and a phenolic proton a 5.76 in the ratios of 6 to 2 to 1.
  • the infrared spectrum showed a strong band at 900 cm. characteristic of 1, 2, 3, 5 benzene substitution which is the order of substitution in 2,6-xylenol-4-sulfonyl chloride when numbering is started from the methyl group In the 6-position
  • Example III This example illustrates the polymerization of 2,6- xylenol-4-sulfonyl chloride to poly(2,6-xylyl-4-sulfonate).
  • the polymer was extracted with approximately 200 ml. of acetone to remove low molecular weight polymer and unreacted monomers. Analysis of the acetone insoluble polymer showed 51.9% C, 4.5% H and 15.9% S which compares very favorably with the calculated values of 51.6% C, 4.3% H and 17.2% S. The intrinsic viscosity of this polymer measured in nitrobenzene at 25 C. is 0.57.
  • the polymer was pressed into a film at 260 C. and quenched in ice water to prevent crystallization. Samples of the resulting flexible, clear film showed no change when allowed to stand for two weeks at 90 C. in 0.5 N hydrochloric acid or 0.5 N potassium hydroxide. The X-ray analysis showed the film was amorphous.
  • Crystallization of the film can be obtained by exposing it to a solvent such as acetone.
  • the film can be cold-drawn in one or both directions to produce a molecularly oriented film.
  • fibers can be drawn from solutions or melts of the polymer.
  • the 2,6- xylenol-3-sulfonyl chloride and the mixture of 2,6-xylenol- 3-sulfonyl chloride and 2,6-xylenol-4-sulfonyl chloride prepared in Example I is polymerized to high molecular weight polymers having the properties similar to the 4- isomer but less crystalline in nature.
  • the copolymer pre-' pared from the mixture of 2,6-xylenol-3-sulfonyl chloride and 2,6-xylenol-4-sulfonyl chloride is noticeably less crystalline because of the random order of the two isomeric units in the polymer molecule.
  • the poly(2,6-xylyl-4-sulfonate), poly(2,6-xylyl-3-sulfo hate), and copolymers of these two polymers of this invention have a wide variety of uses; as coating compositions they may be coated onto metallic or nonmetallic substrates, by flame spraying, melt casting, or by casting while dissolved in one of the solvents in which it is made, or other solvent in which it is soluble, and thereafter evaporating the solvent at an elevated temperature, and if de sired, at reduced pressure.
  • the hot solution of the solvent may be forced through a spinneret into a heated drying tower, preferably maintained at a reduced pressure, to form filaments or fibers, or the molten polymer may be forced through spinnerets by well known techniques to form filaments and fibers.
  • the fibers so formed may be formed into yarns or used to form fiber matting.
  • the poly(2,6-Xylylsulfonates) may be cast from solution or from the melt of the polymer, extruded through a die or otherwise sheeted to form a continuous film of the polymers.
  • the compositions may also be injection, transfer, or compression molded under heat and pressure to form intricately shaped objects of Wide utility, dependent on the particular object molded.
  • these films and fabrics or mats made from the fibers include a wide variety of electrical applications, that is, as a dielec tric, for example, as a dielectric in capacitors, as slot insulation for motors, primary insulation for heat-resistant wire, pressure-sensitive electrical tape, split mica insulating tape, i.e., mica sheet laminated or bonded with the polymer, small condensers, metal foil laminated to the film or film having an adherent metal coating, weather resistant electrical wire, i.e., a conductor wrapped with film coated with asphalt, as a wrapping for submerged pipe to insulate against ground currents, as primary and secondary insulation in transformer construction, as a dielectric in electro-luminescent structures, etc.
  • electrical applications that is, as a dielec tric, for example, as a dielectric in capacitors, as slot insulation for motors, primary insulation for heat-resistant wire, pressure-sensitive electrical tape, split mica insulating tape, i.e., mica sheet laminated or bonded with the polymer, small conden
  • An essentially linear polymer selected from the group consisting of poly(2,6-xylyl-3-sulfonate), having the structural formula and copolymers consisting essentially of 2,6-xylyl-3-sulfonate and 2,6-xylyl-4-sulfonate structural units, said c0- polymers have the structural formula where n is at least 55.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
US429652A 1965-02-01 1965-02-01 Product and process for preparing poly(2, 6-xylylsulfonates) Expired - Lifetime US3337512A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US429652A US3337512A (en) 1965-02-01 1965-02-01 Product and process for preparing poly(2, 6-xylylsulfonates)
GB2556/66A GB1126004A (en) 1965-02-01 1966-01-19 Xylenol sulfonyl chlorides and polymers made therefrom
NL6600874A NL6600874A (enrdf_load_stackoverflow) 1965-02-01 1966-01-24
DE19661595720 DE1595720A1 (de) 1965-02-01 1966-01-27 Verfahren zur Herstellung von Poly(2,6-xylylensulfonaten)
FR48006A FR1466814A (fr) 1965-02-01 1966-02-01 Chlorures de xylénolsulfonyle, polymères produits par auto-condensation de ces composés, et procédés pour leur préparation
US631849A US3530177A (en) 1965-02-01 1967-04-19 2,6-xylenol-3-sulfonyl chloride and 2,6-xylenol-4-sulfonyl chloride

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US429652A US3337512A (en) 1965-02-01 1965-02-01 Product and process for preparing poly(2, 6-xylylsulfonates)

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NL (1) NL6600874A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549595A (en) * 1969-03-11 1970-12-22 Phillips Petroleum Co Poly(phenylenesulfonate) resin and method of preparation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB830822A (en) * 1956-05-02 1960-03-23 Merck & Co Inc Substituted phenols

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB830822A (en) * 1956-05-02 1960-03-23 Merck & Co Inc Substituted phenols

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549595A (en) * 1969-03-11 1970-12-22 Phillips Petroleum Co Poly(phenylenesulfonate) resin and method of preparation

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GB1126004A (en) 1968-09-05
DE1595720A1 (de) 1970-04-30
NL6600874A (enrdf_load_stackoverflow) 1966-08-02

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